Deposition of low-k films

ABSTRACT

Methods for atomic layer deposition (ALD) of plasma enhanced atomic layer deposition (PEALD) of low-K films are described. A method of depositing a film comprises exposing a substrate to a silicon precursor having the general formulae (Ia), (Ib), (Ic), (Id), (IX), or (X) 
     
       
         
         
             
             
         
       
     
     wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8  are independently selected from hydrogen (H), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, and substituted or unsubstituted vinyl, X is silicon (Si) or carbon (C), Y is carbon (C) or oxygen (O), R 9 , R 10 , R 11 , R 12  R 13 , R 14 , R 15 , and R 16  are independently selected from hydrogen (H), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted vinyl, silane, substituted or unsubstituted amine, or halide; and exposing the substrate to an oxidant to react with the silicon-containing film to form one or more of a silicon oxycarbide (SiOC) film or a silicon oxycarbonitride (SiOCN) film on the substrate, the oxidant comprising one or more of a carboxylic acid, an aldehyde, a ketone, an ethenediol, an oxalic acid, a glyoxylic acid, a peroxide, an alcohol, and a glyoxal.

TECHNICAL FIELD

Embodiments of the present disclosure pertain to the field of electronicdevice manufacturing, and in particular, to integrated circuit (IC)manufacturing. More particularly, embodiments of the disclosure providemethods of depositing low-K films.

BACKGROUND

Integrated circuits have evolved into complex devices that can includemillions of transistors, capacitors, and resistors on a single chip. Theevolution of chip designs continually requires faster circuitry andgreater circuit density. The demands for faster circuits with greatercircuit densities impose corresponding demands on the materials used tofabricate such integrated circuits. In particular, as the dimensions ofintegrated circuit components are reduced, it is necessary to use lowresistivity conductive materials as well as low dielectric constantinsulating materials to obtain suitable electrical performance from suchcomponents.

Atomic Layer Deposition (ALD) and Plasma-Enhanced ALD (PEALD) aredeposition techniques that offer control of film thickness andconformality. Most ALD processes are based on binary reaction sequences,where each of the two surface reactions occurs sequentially. Because thesurface reactions are sequential, the two gas phase reactants are not incontact, and possible gas phase reactions that may form and depositparticles are limited. Due to continuously decreasing device dimensionsin the semiconductor industry, there is increasing interest andapplications that use ALD/PEALD.

Low-k silicon-based dielectric films are important for themicroelectronics manufacturing, e.g. as a spacer with low wet etch rate(about 0 A/min in 1:100 HF) and a k-value of about. The spacer shouldalso maintain a low etch rate after being exposed to a moderate oxygen(O₂) plasma (2 KW remote plasma). Historically, silicon-based low-kfilms have been deposited by ALD in a furnace chamber. To achieve thedesired film properties, the film needs to be deposited at temperaturesabove 500° C. With thermal budgets continually decreasing with everychip node, there is a need for the deposition of low-k films attemperatures below 500° C. Depositing silicon oxycarbide (SiOC) films byALD using oxidation sources such as water or oxygen may result in a filmwith low carbon. In order to decrease etch rates, carbon levels need tobe below 10% of the film.

Accordingly, there is a need for new deposition methods for siliconoxycarbide (SiOC) and silicon oxycarbonitride (SiOCN).

SUMMARY

Methods to manufacture integrated circuits are described. In one or moreembodiments, a method of depositing a film on a substrate is described.The method comprises: exposing a substrate in a processing chamber to asilicon precursor to deposit a silicon-containing film on the substrate,the silicon precursor having a structure of general formulae (Ia), (Ib),(Ic), (Id), (IX), or (X)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl, X issilicon (Si) or carbon (C), Y is carbon (C) or oxygen (O), R⁹, R¹⁰, R¹¹,R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected from hydrogen (H),substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy,substituted or unsubstituted vinyl, silane, substituted or unsubstitutedamine, or halide; purging the processing chamber of the siliconprecursor; exposing the substrate to an oxidant to react with thesilicon-containing film to form one or more of a silicon oxycarbide(SiOC) film or a silicon oxycarbonitride (SiOCN) film on the substrate,the oxidant comprising one or more of a carboxylic acid, an aldehyde, aketone, an ethenediol, an oxalic acid, a glyoxylic acid, a peroxide, analcohol, and a glyoxal; and purging the processing chamber of theoxidant.

In one or more embodiments, a method of depositing a film comprises:exposing a substrate to a silicon precursor of general formulae (Ia),(Ib), (Ic), (Id), (IX), or (X)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl, X issilicon (Si) or carbon (C), Y is carbon (C) or oxygen (O), R⁹, R¹⁰, R¹¹,R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected from hydrogen (H),substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy,substituted or unsubstituted vinyl, silane, substituted or unsubstitutedamine, or halide to form a silicon-containing film; exposing thesubstrate to an oxidant to react with the silicon-containing film toform one or more of a silicon oxycarbide (SiOC) film or a siliconoxycarbonitride (SiOCN) film on the substrate; and exposing thesubstrate to one or more of a strong oxidant or oxygen (O₂) plasma, thestrong oxidant selected from one or more of ozone (O₃) and water (H₂O).

One or more embodiments are directed to a method of forming ananolaminate. In one or more embodiments, the method comprises: a firstdeposition cycle and a second deposition cycle. The first depositioncycle comprises: exposing a substrate to a first silicon precursor ofgeneral formulae (Ia), (Ib), (Ic), and (Id):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl to form asilicon-containing film, and exposing the substrate to a first oxidantto react with the silicon-containing film to form one or more of asilicon oxycarbide (SiOC) film or a silicon oxycarbonitride (SiOCN) filmon the substrate. The second deposition cycle comprises: exposing thesubstrate with one or more of the silicon oxycarbide (SiOC) film or thesilicon oxycarbonitride (SiOCN) film thereon to a second siliconprecursor having general formula (IXI) or general formula (X)

wherein X is silicon (Si) or carbon (C), Y is carbon (C) or oxygen (O),R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected fromhydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, substituted or unsubstituted vinyl, silane,substituted or unsubstituted amine, or halide to deposit a secondsilicon-containing film on the substrate; exposing the substrate to asecond plasma to react with the second and silicon-containing film toform one or more of a silicon oxycarbide (SiOC) nanolaminate or asilicon oxycarbonitride (SiOCN) nanolaminate on the substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentdisclosure can be understood in detail, a more particular description ofthe disclosure, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this disclosure and are therefore not to beconsidered limiting of its scope, for the disclosure may admit to otherequally effective embodiments. The embodiments as described herein areillustrated by way of example and not limitation in the figures of theaccompanying drawings in which like references indicate similarelements.

FIG. 1 depicts a flow diagram of a method for forming a low-K film on asubstrate in accordance with one or more embodiments; and

FIG. 2 depicts a flow diagram of a method for forming a low-K film on asubstrate in accordance with one or more embodiments.

DETAILED DESCRIPTION

Before describing several exemplary embodiments of the disclosure, it isto be understood that the disclosure is not limited to the details ofconstruction or process steps set forth in the following description.The disclosure is capable of other embodiments and of being practiced orbeing carried out in various ways.

Many of the details, dimensions, angles and other features shown in theFigures are merely illustrative of particular embodiments. Accordingly,other embodiments can have other details, components, dimensions, anglesand features without departing from the spirit or scope of the presentdisclosure. In addition, further embodiments of the disclosure can bepracticed without several of the details described below.

A “substrate”, “substrate surface”, or the like, as used herein, refersto any substrate or material surface formed on a substrate upon whichprocessing is performed. For example, a substrate surface on whichprocessing can be performed include, but are not limited to, materialssuch as silicon, silicon oxide, strained silicon, silicon on insulator(SOI), carbon doped silicon oxides, silicon nitride, doped silicon,germanium, gallium arsenide, glass, sapphire, and any other materialssuch as metals, metal nitrides, metal alloys, and other conductivematerials, depending on the application. Substrates include, withoutlimitation, semiconductor wafers. Substrates may be exposed to apretreatment process to polish, etch, reduce, oxidize, hydroxylate (orotherwise generate or graft target chemical moieties to impart chemicalfunctionality), anneal and/or bake the substrate surface. In addition toprocessing directly on the surface of the substrate itself, in thepresent disclosure, any of the film processing steps disclosed may alsobe performed on an underlayer formed on the substrate as disclosed inmore detail below, and the term “substrate surface” is intended toinclude such underlayer as the context indicates. Thus for example,where a film/layer or partial film/layer has been deposited onto asubstrate surface, the exposed surface of the newly deposited film/layerbecomes the substrate surface. What a given substrate surface compriseswill depend on what materials are to be deposited, as well as theparticular chemistry used.

As used in this specification and the appended claims, the terms“reactive compound,” “reactive gas,” “reactive species,” “precursor,”“process gas,” and the like are used interchangeably to mean a substancewith a species capable of reacting with the substrate surface ormaterial on the substrate surface in a surface reaction (e.g.,chemisorption, oxidation, reduction). For example, a first “reactivegas” may simply adsorb onto the surface of a substrate and be availablefor further chemical reaction with a second reactive gas.

As used in this specification and the appended claims, the terms“precursor”, “reactant”, “reactive gas” and the like are usedinterchangeably to refer to any gaseous species that can react with thesubstrate surface.

In one or more embodiments, provided is an atomic layer deposition (ALD)process for forming low-K films, e.g. spacer films, using organosilaneprecursors. In one or more embodiments, the silicon precursors are ofgeneral formulae (Ia), (Ib), (Ic), and (Id):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl.

In one or more embodiments, the silicon precursor is any siliconprecursor of general formula (IX) or general formula (X)

wherein X is silicon (Si) or carbon (C), Y is carbon (C) or oxygen (O),R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected fromhydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, substituted or unsubstituted vinyl, silane,substituted or unsubstituted amine, or halide that can react with (i.e.,adsorb or chemisorb onto) the surface to leave a silicon-containingspecies on the surface.

In one or more embodiments X is silicon (Si). In one or moreembodiments, X is carbon (C). In one or more embodiments Y is carbon(C). In one or more embodiments, Y is oxygen (O). In one or moreembodiments, at least one of R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶comprises a substituted or unsubstituted amine. In one or moreembodiments, at least one of R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶comprises —NR^(c)R^(d) where R^(c) and R^(d) independently comprise C₁₋₈alkyl or C₁₋₈ aryl. In one or more embodiments, at least one of R⁹, R¹⁰,R¹¹, R¹² R¹³, R¹⁴, R¹, and R¹⁶ comprises —NMe₂. As recognized by one ofskill in the art, the group —NMe₂ is a dimethyl amine, wherein thelinkage to the compound of general formula (IX) or general formula (X)occurs through the nitrogen atom.

“Atomic layer deposition” or “cyclical deposition” as used herein refersto the sequential exposure of two or more reactive compounds to deposita layer of material on a substrate surface. As used in thisspecification and the appended claims, the terms “reactive compound”,“reactive gas”, “reactive species”, “precursor”, “process gas” and thelike are used interchangeably to mean a substance with a species capableof reacting with the substrate surface or material on the substratesurface in a surface reaction (e.g., chemisorption, oxidation,reduction). The substrate, or portion of the substrate, is exposedseparately to the two or more reactive compounds which are introducedinto a reaction zone of a processing chamber.

In a time-domain ALD process, exposure to each reactive compound isseparated by a time delay to allow each compound to adhere and/or reacton the substrate surface and then be purged from the processing chamber.In a spatial ALD process, different portions of the substrate surface,or material on the substrate surface, are exposed simultaneously to thetwo or more reactive compounds so that any given point on the substrateis substantially not exposed to more than one reactive compoundsimultaneously. As used in this specification and the appended claims,the term “substantially” used in this respect means, as will beunderstood by those skilled in the art, that there is the possibilitythat a small portion of the substrate may be exposed to multiplereactive gases simultaneously due to diffusion, and that thesimultaneous exposure is unintended.

In time-domain ALD embodiments, exposure to each of the process gasesare separated by a time delay/pause to allow the components of theprocess gases to adhere and/or react on the substrate surface.Alternatively, or in combination, in some embodiments, a purge may beperformed before and/or after the exposure of the substrate to theprocess gases, wherein an inert gas is used to perform the purge. Forexample, a first process gas may be provided to the process chamberfollowed by a purge with an inert gas. Next, a second process gas may beprovided to the process chamber followed by a purge with an inert gas.In some embodiments, the inert gas may be continuously provided to theprocess chamber and the first process gas may be dosed or pulsed intothe process chamber followed by a dose or pulse of the second processgas into the process chamber. In such embodiments, a delay or pause mayoccur between the dose of the first process gas and the second processgas, allowing the continuous flow of inert gas to purge the processchamber between doses of the process gases.

In one aspect of a time-domain ALD process, a first reactive gas (i.e.,a first precursor or compound A) is pulsed into the reaction zonefollowed by a first time delay. Next, a second precursor or compound Bis pulsed into the reaction zone followed by a second delay. During eachtime delay, a purge gas, such as argon, is introduced into theprocessing chamber to purge the reaction zone or otherwise remove anyresidual reactive compound or reaction by-products from the reactionzone. Alternatively, the purge gas may flow continuously throughout thedeposition process so that only the purge gas flows during the timedelay between pulses of reactive compounds. The reactive compounds arealternatively pulsed until a desired film or film thickness is formed onthe substrate surface. In either scenario, the ALD process of pulsingcompound A, purge gas, compound B and purge gas is a cycle. A cycle canstart with either compound A or compound B and continue the respectiveorder of the cycle until achieving a film with the predeterminedthickness.

In one or more embodiments, the purge gas is selected from one or moreof argon (Ar), nitrogen (N₂), or helium (He). In one or moreembodiments, the same purge gas is used to purge the precursor and theoxidant. In other embodiments, a different purge gas is used to purgethe processing chamber of the precursor than the purge gas used to purgethe processing chamber of the oxidant.

In an embodiment of a spatial ALD process, a first reactive gas andsecond reactive gas are delivered simultaneously to the reaction zonebut are separated by an inert gas curtain and/or a vacuum curtain. Thesubstrate is moved relative to the gas delivery apparatus so that anygiven point on the substrate is exposed to the first reactive gas andthe second reactive gas.

In spatial ALD embodiments, exposure to each of the process gases occurssimultaneously to different parts of the substrate so that one part ofthe substrate is exposed to the first reactive gas while a differentpart of the substrate is exposed to the second reactive gas (if only tworeactive gases are used). The substrate is moved relative to the gasdelivery system so that each point on the substrate is sequentiallyexposed to both the first and second reactive gases. In any embodimentof a time-domain ALD or spatial ALD process, the sequence may berepeated until a predetermined layer thickness is formed on thesubstrate surface.

A “pulse” or “dose” as used herein is intended to refer to a quantity ofa source gas that is intermittently or non-continuously introduced intothe process chamber. The quantity of a particular compound within eachpulse may vary over time, depending on the duration of the pulse. Aparticular process gas may include a single compound or amixture/combination of two or more compounds, for example, the processgases described below.

The durations for each pulse/dose are variable and may be adjusted toaccommodate, for example, the volume capacity of the processing chamberas well as the capabilities of a vacuum system coupled thereto.Additionally, the dose time of a process gas may vary according to theflow rate of the process gas, the temperature of the process gas, thetype of control valve, the type of process chamber employed, as well asthe ability of the components of the process gas to adsorb onto thesubstrate surface. Dose times may also vary based upon the type of layerbeing formed and the geometry of the device being formed. A dose timeshould be long enough to provide a volume of compound sufficient toadsorb/chemisorb onto substantially the entire surface of the substrateand form a layer of a process gas component thereon.

Plasma enhanced atomic layer deposition (PEALD) is a widely usedtechnique for depositing thin films on a substrate. In some examples ofPEALD processes, a material may be formed from the same chemicalprecursors as thermal ALD processes, but at a higher deposition rate anda lower temperature. A PEALD process, in general, provides that areactant gas and a reactant plasma are sequentially introduced into aprocess chamber containing a substrate. The first reactant gas is pulsedin the process chamber and is adsorbed onto the substrate surface.Thereafter, the reactant plasma is pulsed into the process chamber andreacts with the first reactant gas to form a deposition material, e.g. athin film on a substrate. Similarly to a thermal ALD process, a purgestep maybe conducted between the delivery of each of the reactants.Embodiments described herein in reference to a PEALD process can becarried out using any suitable thin film deposition system. Anyapparatus description described herein is illustrative and should not beconstrued or interpreted as limiting the scope of the embodimentsdescribed herein.

Plasma enhanced chemical vapor deposition (PECVD) is used to depositthin films due to cost efficiency and film property versatility. In aPECVD process, for example, a hydrocarbon source, such as a gas-phasehydrocarbon or a vapor of a liquid-phase hydrocarbon that have beenentrained in a carrier gas, is introduced into a PECVD chamber. Aplasma-initiated gas, typically helium, is also introduced into thechamber. Plasma is then initiated in the chamber to create excitedCH-radicals. The excited CH-radicals are chemically bound to the surfaceof a substrate positioned in the chamber, forming the desired filmthereon. Embodiments described herein in reference to a PECVD processcan be carried out using any suitable thin film deposition system. Anyapparatus description described herein is illustrative and should not beconstrued or interpreted as limiting the scope of the embodimentsdescribed herein.

In some embodiments, the films described herein may be formed by atomiclayer deposition (plasma enhanced and/or thermal) processes using asilicon precursor including one or more precursor of general formulae(Ia), (Ib), (Ic), and (Id):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl that canreact with (i.e., adsorb or chemisorb onto) the substrate surface toleave a silicon-containing species on the substrate surface.

In other embodiments, the films described herein may be formed using asilicon precursor including one or more precursor of general formula(XX)

Si(NR^(a)R^(b))_(z)

R^(a) and R^(b), are independently selected from hydrogen (H),substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy,and substituted or unsubstituted vinyl, and z is an integer in a rangeof from 1 to 4. The precursor of general Formula (XX) can react with(i.e., adsorb or chemisorb onto) the substrate surface to leave asilicon-containing species on the substrate surface.

In other embodiments, the silicon precursor is any silicon precursor ofgeneral formula (IX) or general formula (X)

wherein X is silicon (Si) or carbon (C), Y is carbon (C) or oxygen (O),R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected fromhydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, substituted or unsubstituted vinyl, silane,substituted or unsubstituted amine, or halide that can react with (i.e.,adsorb or chemisorb onto) the surface to leave a silicon-containingspecies on the surface.

In one or more embodiments X is silicon (Si). In one or moreembodiments, X is carbon (C). In one or more embodiments Y is carbon(C). In one or more embodiments, Y is oxygen (O). In one or moreembodiments, at least one of R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶comprises a substituted or unsubstituted amine. In one or moreembodiments, at least one of R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶comprises —NR^(c)R^(d) where R^(c) and R^(d) independently comprise C₁₋₈alkyl or C₁₋₈ aryl. In one or more embodiments, at least one of R⁹, R¹⁰,R¹¹, R¹² R¹³, R¹⁴, R¹, and R¹⁶ comprises —NMe₂. As recognized by one ofskill in the art, the group —NMe₂ is a dimethyl amine, wherein thelinkage to the compound of general formula (IX) or general formula (X)occurs through the nitrogen atom.

Unless otherwise indicated, the term “lower alkyl,” “alkyl,” or “alk” asused herein alone or as part of another group includes both straight andbranched chain hydrocarbons, containing 1 to 20 carbons, in the normalchain, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl,isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl,2,2,4-trimethyl-pentyl, nonyl, decyl, undecyl, dodecyl, the variousbranched chain isomers thereof, and the like. Such groups may optionallyinclude up to 1 to 4 substituents. The alkyl may be substituted orunsubstituted.

As used herein, the term “alkoxy” includes any of the above alkyl groupslinked to an oxygen atom. The alkoxy may be substituted orunsubstituted.

As used herein, the terms “vinyl” or “vinyl-containing” refer to groupscontaining the vinyl group (—CH═CH₂). The vinyl may be substituted orunsubstituted.

As used herein, the term “amine” relates to any organic compoundcontaining at least one basic nitrogen atom, e.g. NR′₂, wherein R′ isindependently selected from hydrogen (H) or alkyl. The alkyl of theamine may be substituted or unsubstituted.

As used herein, the term “silane” refers to a compound SiR′₃, wherein R′is independently selected from hydrogen (H) or alkyl. The alkyl of thesilane may be substituted or unsubstituted.

As used herein, the term “halide” refers to a binary phase, of which onepart is a halogen atom and the other part is an element or radical thatis less electronegative than the halogen, to make a fluoride, chloride,bromide, or iodide compound. A halide ion is a halogen atom bearing anegative charge. As known to those of skill in the art, a halide anionincludes fluoride (F—), chloride (Cl—), bromide (Br—), and iodide.

The deposition process may be carried out at temperatures ranging fromabout 200° C. to about 650° C., including about 225° C., about 250° C.,about 275° C., about 300° C., about 325° C., about 350° C., about 375°C., about 400° C., about 425° C., about 450° C., about 475° C., about500° C., about 525° C., about 550° C., about 575° C., about 600° C.,about 625° C., and about 650° C.

The deposition process may be carried out in a process volume atpressures ranging from 0.1 mTorr to 500 Torr, including a pressure ofabout 0.1 mTorr, about 10 mTorr, about 100 mTorr, about 1000 mTorr,about 5000 mTorr, about 10 Torr, about 20 Torr, about 30 Torr, about 40Torr, about 50 Torr, about 60 Torr, about 70 Torr, about 80 Torr, about90 Torr, about 100 Torr, about 150 Torr, about 200 Torr, about 250 Torr,about 300 Torr, about 350 Torr, about 400 Torr, about 350 Torr, andabout 500 Torr.

In one or more embodiments, the silicon precursor is flowed into theprocessing chamber as a gas. In one or more embodiments, theprecursor-containing gas further includes one or more of a dilution gasselected from helium (He), argon (Ar), xenon (Xe), nitrogen (N₂), orhydrogen (H₂). The dilution gas of some embodiments comprises a compoundthat is inert gas relative to the reactants and substrate materials.

In one or more embodiments, the precursor-containing gas furtherincludes etchant gases such as Cl₂, CF₄, or NF₃ to improve film quality.

In one or more embodiments, the oxidant comprises one or more of theoxidant comprising one or more of a carboxylic acid, an aldehyde, aketone, an ethenediol, an oxalic acid, a glyoxylic acid, a peroxide, analcohol, and a glyoxal.

In one or more embodiments, the oxidant comprises a structure of Formula(II), Formula (III), Formula (IV), Formula (V), Formula (VI), Formula(VII), and Formula (VIII):

wherein R is selected from the group consisting of C₁-C₆ alkyl, C₁-C₆alkene, C₁-C₆ alkyne, C₅-C₈ aryl, and n is an integer from −1 to 6. Insome embodiments, n is an integer selected from −1, 0, 1, 2, 3, 4, 5,and 6. In other embodiments, n is an integer in a range of from 1 to 6and includes 1, 2, 3, 4, 5, and 6.

As used herein, the term “alkene” or “alkenyl” or “lower alkenyl” refersto straight or branched chain radicals of 2 to 20 carbons, or 2 to 12carbons, and 1 to 8 carbons in the normal chain, which include one tosix double bonds in the normal chain, such as vinyl, 2-propenyl,3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl,2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl,3-undecenyl, 4-dodecenyl, 4,8,12-tetradecatrienyl, and the like, andwhich may be optionally substituted with 1 to 4 substituents, namely,halogen, haloalkyl, alkyl, alkoxy, alkenyl, alkynyl, aryl, arylalkyl,cycloalkyl, amino, hydroxy, heteroaryl, cycloheteroalkyl, alkanoylamino,alkylamido, arylcarbonyl-amino, nitro, cyano, thiol, alkylthio, and/orany of the alkyl substituents set out herein.

As used herein, the term “alkynyl” or “lower alkynyl” refers to straightor branched chain radicals of 2 to 20 carbons, or 2 to 12 carbons, or 2to 8 carbons in the normal chain, which include one triple bond in thenormal chain, such as 2-propynyl, 3-butynyl, 2-butynyl, 4-pentynyl,3-pentynyl, 2-hexynyl, 3-hexynyl, 2-heptynyl, 3-heptynyl, 4-heptynyl,3-octynyl, 3-nonynyl, 4-decynyl, 3-undecynyl, 4-dodecynyl, and the like,and which may be optionally substituted with 1 to 4 substituents,namely, halogen, haloalkyl, alkyl, alkoxy, alkenyl, alkynyl, aryl,arylalkyl, cycloalkyl, amino, heteroaryl, cycloheteroalkyl, hydroxy,alkanoylamino, alkylamido, arylcarbonylamino, nitro, cyano, thiol,and/or alkylthio, and/or any of the alkyl substituents set out herein.

As used herein, the term “aryl” refers to monocyclic and bicyclicaromatic groups containing 6 to 10 carbons in the ring portion (such asphenyl, biphenyl or naphthyl, including 1-naphthyl and 2-naphthyl) andmay optionally include 1 to 3 additional rings fused to a carbocyclicring or a heterocyclic ring (such as aryl, cycloalkyl, heteroaryl, orcycloheteroalkyl rings). The aryl group may be optionally substitutedthrough available carbon atoms with 1, 2, or 3 substituents, forexample, hydrogen, halo, haloalkyl, alkyl, haloalkyl, alkoxy,haloalkoxy, alkenyl, trifluoromethyl, trifluoromethoxy, alkynyl, and thelike.

The term “halogen” or “halo” as used herein alone or as part of anothergroup refers to chlorine (Cl), bromine (Br), fluorine (F), and iodine(I), as well as CF₃.

In one or more embodiments, the low-K dielectric film may be depositedto a thickness greater than about 0.1 nm. In other embodiments, thelow-K dielectric film may be deposited to a thickness in a range ofabout 0.1 nm to about 100 nm, or about 0.5 nm to about 100 nm, includingabout 0.1 nm, about 1 nm, about 10 nm, about 20 nm, about 25 nm, about30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm,about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about85 nm, about 90 nm, about 95 nm, or about 100 nm.

In one or more embodiments, a low-k film is deposited on a substrate.The low-k film of one or more embodiments, advantageously has a wet etchrate (WER) in range of about 0.1 Å/min to about 10 Å/min in hydrofluoricacid (1:100 HF), including about 0.1 Å/min, about 0.5 Å/min, about 1Å/min, about 2 Å/min, about 3 Å/min, about 4 Å/min, about 5 Å/min, about6 Å/min, about 7 Å/min, about 8 Å/min, about 9 Å/min, and about 10Å/min. The low-k film of one or more embodiments, advantageously hashigh ashing resistance. In one or more embodiments, the low-k film has adielectric constant or extinction coefficient or k-value in a range ofabout 2.0 to about 6.0, including about 2.25, about 2.5, about 2.75,about 3.0, about 3.25, about 3.5, about 3.75, about 4.0, about 4.25,about 4.5, about 4.75, about 5.0, about 5.25, about 5.5, about 5.75, orabout 6.0.

In one or more embodiments, the density of the low-K film is greaterthan about 2.1 g/cc.

With reference to FIG. 1, one or more embodiments of the disclosure aredirected to method 100 of depositing a thin film. The method illustratedin FIG. 1 is representative of an atomic layer deposition (ALD) processin which the substrate or substrate surface is exposed sequentially tothe reactive gases in a manner that prevents or minimizes gas phasereactions of the reactive gases. In some embodiments, the methodcomprises a chemical vapor deposition (CVD) process in which thereactive gases are mixed in the processing chamber to allow gas phasereactions of the reactive gases and deposition of the thin film. In someembodiments, the method comprises a plasma enhanced atomic layerdeposition (PEALD process).

In some embodiments, the method 100 includes a pre-treatment operation105. The pre-treatment can be any suitable pre-treatment known to theskilled artisan. Suitable pre-treatments include, but are not limitedto, pre-heating, cleaning, soaking, native oxide removal, or depositionof an adhesion layer (e.g. titanium nitride (TiN)). In one or moreembodiments, an adhesion layer, such as titanium nitride, is depositedat pre-treatment operation 105.

At deposition operation 110, a process is performed to deposit asilicon-containing thin film on the substrate (or substrate surface).The deposition process can include one or more operations to form a filmon the substrate. In operation 112, the substrate (or substrate surface)is exposed to a silicon precursor to deposit a film on the substrate (orsubstrate surface). In one or more embodiments, the silicon precursor isany silicon precursor of general formulae (Ia), (Ib), (Ic), and (Id):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl that canreact with (i.e., adsorb or chemisorb onto) the substrate surface toleave a silicon-containing species on the substrate surface. In one ormore embodiments, the silicon precursor comprises

wherein R¹, R², R³, R⁴ are independently selected from hydrogen (H),substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy,and substituted or unsubstituted vinyl that can react with (i.e., adsorbor chemisorb onto) the substrate surface to leave a silicon-containingspecies on the substrate surface. In one or more embodiments, thesilicon precursor comprises

wherein R¹, R², R³, R⁴, R⁵, R⁶ are independently selected from hydrogen(H), substituted or unsubstituted alkyl, substituted or unsubstitutedalkoxy, and substituted or unsubstituted vinyl that can react with(i.e., adsorb or chemisorb onto) the substrate surface to leave asilicon-containing species on the substrate surface. In one or moreembodiments, the silicon precursor comprises

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl that canreact with (i.e., adsorb or chemisorb onto) the substrate surface toleave a silicon-containing species on the substrate surface. In one ormore embodiments, the silicon precursor comprises

wherein R¹, R² are independently selected from hydrogen (H), substitutedor unsubstituted alkyl, substituted or unsubstituted alkoxy, andsubstituted or unsubstituted vinyl that can react with (i.e., adsorb orchemisorb onto) the substrate surface to leave a silicon-containingspecies on the substrate surface.

In other embodiments, the silicon precursor is any silicon precursor ofgeneral formula (IX) or general formula (X)

wherein X is silicon (Si) or carbon (C), Y is carbon (C) or oxygen (O),R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected fromhydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, substituted or unsubstituted vinyl, silane,substituted or unsubstituted amine, or halide that can react with (i.e.,adsorb or chemisorb onto) the surface to leave a silicon-containingspecies on the surface. In one or more embodiments X is silicon (Si). Inone or more embodiments, X is carbon (C). In one or more embodiments Yis carbon (C). In one or more embodiments, Y is oxygen (O). In one ormore embodiments, at least one of R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, andR¹⁶ comprises a substituted or unsubstituted amine. In one or moreembodiments, at least one of R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶comprises —NMe₂. As recognized by one of skill in the art, the group—NMe₂ is a dimethyl amine, wherein the linkage to the compound ofgeneral formula (IX) or general formula (X) occurs through the nitrogenatom.

In one or more embodiments, the silicon precursor comprises one or moreof

or the like.

In some embodiments, the silicon precursor comprises one or more ofbis(diethylamino)silane, bis(dimethylamine)silane,bis(dipropylamino)silane, dimethylamino diethylamino silane,tris(dimethylamino)silane, tetrakis(dimethylamino)silane,1,1-Bis(dimethylamino)-3,3-bis(dimethylamino)siletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-dimethyl-1,3-disiletane,1,1,3,3-Tetrakis(dimethylamino)-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,Bis(tris-dimethylamino)silyl methane, and 1,3-disilacylobutane. As usedin this manner, the term “consists essentially of” means that thesilicon precursor comprises greater than or equal to about 95%, 98%, 99%or 99.5% of comprises one or more of bis(diethylamino)silane,bis(dimethylamine)silane, bis(dipropylamino)silane, dimethylaminodiethylamino silane, tris(dimethylamino)silane,tetrakis(dimethylamino)silane,1,1-Bis(dimethylamino)-3,3-bis(dimethylamino)siletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-dimethyl-1,3-disiletane,1,1,3,3-Tetrakis(dimethylamino)-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,Bis(tris-dimethylamino)silyl methane, and 1,3-disilacylobutane on amolecular basis. The presence of diluent, carrier and/or inert gases,for example, is not taken into consideration in the calculation.

In one or more embodiments, the substrate (or substrate surface) can beany suitable surface. Suitable surfaces include, but are not limited to,silicon (Si), silicon dioxide (SiO₂), silicon oxide (SiO_(x)), siliconoxycarbide (SiOC), platinum (Pt), titanium nitride (TiN), tantalumnitride (TaN), copper (Cu), cobalt (Cu), tungsten (W), ruthenium (Ru),molybdenum (Mo) or combinations thereof.

At operation 114, the processing chamber is purged to remove unreactedsilicon precursor, reaction products and by-products. As used in thismanner, the term “processing chamber” also includes portions of aprocessing chamber adjacent the substrate surface without encompassingthe complete interior volume of the processing chamber. For example, ina sector of a spatially separated processing chamber, the portion of theprocessing chamber adjacent the substrate surface is purged of thesilicon precursor by any suitable technique including, but not limitedto, moving the substrate through a gas curtain to a portion or sector ofthe processing chamber that contains none or substantially none of thesilicon precursor. In some embodiments, purging the processing chambercomprises flowing a purge gas over the substrate. In some embodiments,the portion of the processing chamber refers to a micro-volume or smallvolume process station within a processing chamber. The term “adjacent”referring to the substrate surface means the physical space next to thesurface of the substrate which can provide sufficient space for asurface reaction (e.g., precursor adsorption) to occur.

At operation 116, the substrate (or substrate surface) is exposed to anoxidizing agent (or oxidant) to form one or more of a silicon oxycarbide(SiOC) or silicon oxycarbonitride (SiOCN) film on the substrate. Theoxidizing agent can react with the silicon-containing species (e.g.silicon-containing film) on the substrate surface to form one or more ofa silicon oxycarbide (SiOC) or silicon oxycarbonitride (SiOCN) film. Insome embodiments, the oxidizing agent comprises one or more of acarboxylic acid, an aldehyde, a ketone, an ethenediol, an oxalic acid, aglyoxylic acid, a peroxide, an alcohol, and a glyoxal. In someembodiments, the oxidizing agent comprises a structure of Formula (II),Formula (III), Formula (IV), Formula (V), Formula (VI), Formula (VII),and Formula (VIII):

wherein R is selected from the group consisting of C₁-C₆ alkyl, C₁-C₆alkene, C₁-C₆ alkyne, C₅-C₈ aryl, and n is an integer from −1 to 6.

At operation 118, the processing chamber is purged after exposure to theoxidizing agent. Purging the processing chamber in operation 118 can bethe same process or different process than the purge in operation 114.Purging the processing chamber, portion of the processing chamber, areaadjacent the substrate surface, etc., removes unreacted oxidizing agent,reaction products and by-products from the area adjacent the substratesurface.

In some embodiments, the deposition process comprises a plasma enhancedatomic layer deposition process (PEALD). After forming siliconoxycarbide (SiOC) or silicon oxycarbonitride (SiOCN) film on thesubstrate, the substrate may be optionally exposed to a strong oxidantor oxygen (O₂) plasma at operation 120. In one or more embodiments, thestrong oxidant is selected from one or more of ozone (O₃) or water(H₂O).

In one or more embodiments, exposing the silicon oxycarbide (SiOC) orsilicon oxycarbonitride (SiOCN) film to an oxygen (O₂) plasma in theprocessing chamber improves the growth rate and helps maintain a highcarbon content in the silicon oxycarbide (SiOC) or siliconoxycarbonitride (SiOCN) film. In some embodiments, the plasma is aremote plasma. In other embodiments, the plasma is a direct plasma.

In one or more embodiments, the plasma may be generated remotely orwithin the processing chamber. In one or more embodiments, the plasma isan inductively coupled plasma (ICP) or a conductively coupled plasma(CCP). Any suitable power can be used depending on, for example, thereactants, or the other process conditions. In some embodiments, theplasma is generated with a plasma power in the range of about 10 W toabout 3000 W. In some embodiments, the plasma is generated with a plasmapower less than or equal to about 3000 W, less than or equal to about2000 W, less than or equal to about 1000 W, less than or equal to about500 W, or less than or equal to about 250 W.

At operation 122, the processing chamber is purged after exposure to thestrong oxidant or the oxygen (O₂) plasma. Purging the processing chamberin operation 122 can be the same process or different process than thepurge in operation 114 and/or operation 118. Purging the processingchamber, portion of the processing chamber, area adjacent the substratesurface, etc., removes the strong oxidant, plasma, reaction products andby-products from the area adjacent the substrate surface.

At decision 125, the thickness of the deposited film, or number ofcycles of silicon-precursor and oxidizing agent is considered. If thedeposited film has reached a predetermined thickness or a predeterminednumber of process cycles have been performed, the method 100 moves to apost-processing operation 130. If the thickness of the deposited film orthe number of process cycles has not reached the predeterminedthreshold, the method 100 returns to deposition operation 110 to exposethe substrate surface to the silicon precursor again in operation 112,and continuing.

The post-processing operation 130 can be, for example, a process tomodify film properties (e.g., annealing) or a further film depositionprocess (e.g., additional ALD or CVD processes) to grow additionalfilms. In some embodiments, the post-processing operation 130 can be aprocess that modifies a property of the deposited film. In someembodiments, the post-processing operation 130 comprises annealing theas-deposited film. In some embodiments, annealing is done attemperatures in the range of about 300° C., 400° C., 500° C., 600° C.,700° C., 800° C., 900° C. or 1000° C. The annealing environment of someembodiments comprises one or more of an inert gas (e.g., molecularnitrogen (N₂), argon (Ar)) or a reducing gas (e.g., molecular hydrogen(H₂) or ammonia (NH₃)) or an oxidant, such as, but not limited to,oxygen (O₂), ozone (O₃), or peroxides. Annealing can be performed forany suitable length of time. In some embodiments, the film is annealedfor a predetermined time in the range of about 15 seconds to about 90minutes, or in the range of about 1 minute to about 60 minutes. In someembodiments, annealing the as-deposited film increases the density,decreases the resistivity and/or increases the purity of the film.

The method 100 can be performed at any suitable temperature dependingon, for example, the silicon precursor, oxidizing agent or thermalbudget of the device. In some embodiments, exposures to the siliconprecursor (operation 112) and the oxidizing agent (operation 116) occurat the same temperature. In some embodiments, the substrate ismaintained at a temperature in a range of about 200° C. to about 650°C., or in the range of about 350° C. to about 500° C.

In some embodiments, exposure to the silicon precursor (operation 112)occurs at a different temperature than the exposure to the oxidizingagent (operation 116). In some embodiments, the substrate is maintainedat a first temperature in a range of about 300° C. to about 650° C. forthe exposure to the silicon precursor, and at a second temperature inthe range of about 200° C. to about 650° C. for exposure the oxidizingagent.

In the embodiment illustrated in FIG. 1, deposition operation 110 thesubstrate (or substrate surface) is exposed to the silicon precursor andthe oxidizing agent sequentially. In another, un-illustrated,embodiment, the substrate (or substrate surface) is exposed to thesilicon precursor and the oxidizing agent simultaneously in a CVDreaction. In a CVD reaction, the substrate (or substrate surface) can beexposed to a gaseous mixture of the silicon precursor and oxidizingagent to deposit one or more of a silicon oxycarbide (SiOC) or siliconoxycarbonitride (SiOCN) film having a predetermined thickness. In theCVD reaction, one or more of a silicon oxycarbide (SiOC) or siliconoxycarbonitride (SiOCN) film can be deposited in one exposure to themixed reactive gas, or can be multiple exposures to the mixed reactivegas with purges between.

In one or more embodiments, the silicon oxycarbide (SiOC) film has acarbon content of greater than or equal to about 5%, 7.5%, 10%, 12.5 or15%, on an atomic basis. In some embodiments, the silicon oxycarbide(SiOC) film comprises a carbon content in the range of about 2% to about50%, or in the range of about 3% to about 45%, or in the range of about4% to about 40%, on an atomic basis. In some embodiments, the siliconoxycarbide (SiOC) film has no nitrogen present.

In one or more embodiments, the silicon oxycarbonitride (SiOCN) film hasa nitrogen content of greater than or equal to about 0%, 5%, 7.5%, 10%,12.5 or 15%, on an atomic basis. In some embodiments, the siliconoxycarbonitride (SiOCN) film comprises a nitrogen content in the rangeof about 0% to about 40%, or in the range of about 3% to about 35%, orin the range of about 4% to about 30%, on an atomic basis.

The deposition operation 110 can be repeated to form one or more of asilicon oxycarbide (SiOC) or silicon oxycarbonitride (SiOCN) film havinga predetermined thickness. In some embodiments, the deposition operation110 is repeated to provide one or more of a silicon oxycarbide (SiOC) orsilicon oxycarbonitride (SiOCN) film having a thickness greater thanabout 0.1 nm, or in the range of about 0.1 nm to about 1000 nm.

In one or more embodiments, the low-k silicon oxycarbide (SiOC) film orsilicon oxycarbonitride (SiOCN) film is used as a spacer.

With reference to FIG. 2, one or more embodiments of the disclosure aredirected to method 200 of depositing a thin film. The method 200comprises a first deposition cycle 210 and a second deposition cycle220.

In some embodiments, the method 200 includes a pre-treatment operation205. The pre-treatment can be any suitable pre-treatment known to theskilled artisan. Suitable pre-treatments include, but are not limitedto, pre-heating, cleaning, soaking, native oxide removal, or depositionof an adhesion layer (e.g. titanium nitride (TiN)). In one or moreembodiments, an adhesion layer, such as titanium nitride, is depositedat pre-treatment operation 205.

At first deposition cycle 210, a process is performed to deposit asilicon-containing thin film on the substrate (or substrate surface).The deposition process can include one or more operations to form a filmon the substrate. In operation 212, the substrate (or substrate surface)is exposed to a first silicon precursor to deposit a film on thesubstrate (or substrate surface). general formulae (Ia), (Ib), (Ic), and(Id):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl that canreact with (i.e., adsorb or chemisorb onto) the substrate surface toleave a silicon-containing species on the substrate surface.

In some embodiments, the first silicon precursor comprises one or moreof bis(diethylamino)silane, bis(dimethylamine)silane,bis(dipropylamino)silane, dimethylamino diethylamino silane,tris(dimethylamino)silane, and tetrakis(dimethylamino)silane. As used inthis manner, the term “consists essentially of” means that the siliconprecursor comprises greater than or equal to about 95%, 98%, 99% or99.5% of one or more of bis(diethylamino)silane,bis(dimethylamine)silane, bis(dipropylamino)silane, dimethylaminodiethylamino silane, tris(dimethylamino)silane, andtetrakis(dimethylamino)silane. on a molecular basis. The presence ofdiluent, carrier and/or inert gases, for example, is not taken intoconsideration in the calculation.

The processing chamber may then be purged to remove unreacted firstsilicon precursor, reaction products and by-products. At operation 214,the substrate (or substrate surface) is exposed to a first oxidizingagent (or oxidant) to form one or more of a silicon oxycarbide (SiOC) orsilicon oxycarbonitride (SiOCN) film on the substrate. The oxidizingagent can react with the silicon-containing species (e.g.silicon-containing film) on the substrate surface to form one or more ofa silicon oxycarbide (SiOC) or silicon oxycarbonitride (SiOCN) film. Insome embodiments, the first oxidizing agent comprises one or more of acarboxylic acid, an aldehyde, a ketone, an ethenediol, an oxalic acid, aglyoxylic acid, a peroxide, an alcohol, and a glyoxal. In someembodiments, the first oxidizing agent comprises a structure of Formula(II), Formula (III), Formula (IV), Formula (V), Formula (VI), Formula(VII), and Formula (VIII):

wherein R is selected from the group consisting of C₁-C₆ alkyl, C₁-C₆alkene, C₁-C₆ alkyne, C₅-C₈ aryl, and n is an integer from −1 to 6.

The processing chamber may then be purged after exposure to the firstoxidizing agent. Purging the processing chamber can be the same processor different process than the purge after exposure to the first siliconprecursor.

In some embodiments, the deposition process comprises a plasma enhancedatomic layer deposition process (PEALD). After forming siliconoxycarbide (SiOC) or silicon oxycarbonitride (SiOCN) film on thesubstrate, the substrate may be optionally exposed to a strong oxidantor oxygen (O₂) plasma at operation 216. In one or more embodiments, thestrong oxidant is selected from one or more of ozone (O₃) and water(H₂O).

In one or more embodiments, exposing the silicon oxycarbide (SiOC) orsilicon oxycarbonitride (SiOCN) film to an oxygen (O₂) plasma in theprocessing chamber improves the growth rate and helps maintain a highcarbon content in the silicon oxycarbide (SiOC) or siliconoxycarbonitride (SiOCN) film. In some embodiments, the plasma is aremote plasma. In other embodiments, the plasma is a direct plasma.

In one or more embodiments, the plasma may be generated remotely orwithin the processing chamber, as described above with respect to method100. The processing chamber may then be purged after exposure to thestrong oxidant or the oxygen (O₂) plasma. Purging the processing chambercan be the same process or different process than the prior purges.Purging the processing chamber, portion of the processing chamber, areaadjacent the substrate surface, etc., removes the strong oxidant,plasma, reaction products and by-products from the area adjacent thesubstrate surface.

At second deposition cycle 220, a process is performed to deposit asecond silicon-containing thin film on the of the silicon oxycarbide(SiOC) film or the silicon oxycarbonitride (SiOCN) film. The depositionprocess can include one or more operations to form a film on thesubstrate. In operation 222, the substrate with one or more of thesilicon oxycarbide (SiOC) film or the silicon oxycarbonitride (SiOCN)film thereon is exposed to a second silicon precursor to deposit asecond silicon-containing film on the substrate (or substrate surface).In one or more embodiments, the second silicon precursor is any siliconprecursor of general formula (IXI) or general formula (X)

wherein X is silicon (Si) or carbon (C), Y is carbon (C) or oxygen (O),R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected fromhydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, substituted or unsubstituted vinyl, silane,substituted or unsubstituted amine, or halide that can react with (i.e.,adsorb or chemisorb onto) the surface to leave a silicon-containingspecies on the surface.

In one or more embodiments X is silicon (Si). In one or moreembodiments, X is carbon (C). In one or more embodiments Y is carbon(C). In one or more embodiments, Y is oxygen (O). In one or moreembodiments, at least one of R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶comprises a substituted or unsubstituted amine. In one or moreembodiments, at least one of R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶comprises —NR^(c)R^(d) where R^(c) and R^(d) independently comprise C₁₋₈alkyl or C₁₋₈ aryl. In one or more embodiments, at least one of R⁹, R¹⁰,R¹¹, R¹² R¹³, R¹⁴, R¹, and R¹⁶ comprises —NMe₂. As recognized by one ofskill in the art, the group —NMe₂ is a dimethyl amine, wherein thelinkage to the compound of general formula (IX) or general formula (X)occurs through the nitrogen atom.

As used herein, the term “amine” relates to any organic compoundcontaining at least one basic nitrogen atom, e.g. NR′₂, wherein R′ isindependently selected from hydrogen (H) or alkyl. The alkyl of theamine may be substituted or unsubstituted.

As used herein, the term “silane” refers to a compound SiR′₃, wherein R′is independently selected from hydrogen (H) or alkyl. The alkyl of thesilane may be substituted or unsubstituted.

As used herein, the term “halide” refers to a binary phase, of which onepart is a halogen atom and the other part is an element or radical thatis less electronegative than the halogen, to make a fluoride, chloride,bromide, or iodide, compound. A halide ion is a halogen atom bearing anegative charge. As known to those of skill in the art, a halide anionincludes fluoride (F—), chloride (Cl—), bromide (Br—), and iodide (I—).

In one or more embodiments, the second silicon precursor comprises oneor more of

or the like.

In some embodiments, the second silicon precursor comprises one or moreof 1,1-Bis(dimethylamino)-3,3-bis(dimethylamino)siletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-dimethyl-1,3-disiletane,1,1,3,3-Tetrakis(dimethylamino)-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,Bis(tris-dimethylamino)silyl methane, or 1,3-dislacyclobutane. In someembodiments, the silicon precursor consists essentially of1,1-Bis(dimethylamino)-3,3-bis(dimethylamino)siletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-dimethyl-1,3-disiletane,1,1,3,3-Tetrakis(dimethylamino)-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,Bis(tris-dimethylamino)silyl, or 1,3-dislacyclobutane methane. As usedin this manner, the term “consists essentially of” means that the secondsilicon precursor comprises greater than or equal to about 95%, 98%, 99%or 99.5% of 1,1-Bis(dimethylamino)-3,3-bis(dimethylamino)siletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-dimethyl-1,3-disiletane,1,1,3,3-Tetrakis(dimethylamino)-1,3-disiletane,1,3-Bis(dimethylamino)-1,3-divinyl-1,3-disiletane,Bis(tris-dimethylamino)silyl methane, or 1,3-dislacyclobutane, on amolecular basis. The presence of diluent, carrier and/or inert gases,for example, is not taken into consideration in the calculation.

The processing chamber may then be purged to remove unreacted secondsilicon precursor, reaction products and by-products. At operation 224,the surface is exposed to a second plasma. In one or more embodiments,the second plasma comprises one or more of nitrogen (N₂), argon (Ar),helium (He), hydrogen (H₂), carbon monoxide (CO), or carbon dioxide(CO₂). In some embodiments, the second plasma is a remote plasma. Inother embodiments, the second plasma is a direct plasma.

In one or more embodiments, the second plasma may be generated remotelyor within the processing chamber. In one or more embodiments, the secondplasma is an inductively coupled plasma (ICP) or a conductively coupledplasma (CCP). Any suitable power can be used depending on, for example,the reactants, or the other process conditions. In some embodiments, thesecond plasma is generated with a plasma power in the range of about 10W to about 3000 W. In some embodiments, the second plasma is generatedwith a plasma power less than or equal to about 3000 W, less than orequal to about 2000 W, less than or equal to about 1000 W, less than orequal to about 500 W, or less than or equal to about 250 W.

The processing chamber may be purged after exposure to the secondplasma. Purging the processing chamber in operation can be the sameprocess or different process than the prior purge processes. Purging theprocessing chamber, portion of the processing chamber, area adjacent thesubstrate surface, etc., removes second plasma, reaction products andby-products from the area adjacent the substrate surface.

At decision 225, the thickness of the nanolaminate film, or number ofcycles of silicon-precursor(s) and oxidizing agent is considered. If thenanolaminate has reached a predetermined thickness or a predeterminednumber of process cycles have been performed, the method 200 moves to apost-processing operation 230. If the thickness of the nanolaminate filmor the number of process cycles has not reached the predeterminedthreshold, the method 200 returns to first deposition cycle 210 orsecond deposition cycle 220 to expose the substrate surface to thesilicon precursor(s) again in operation 212, and continuing or inoperation 222 and continuing. In one or more embodiments, one or more ofthe first deposition cycle or the second deposition cycle may berepeated to form one or more of the silicon oxycarbide (SiOC)nanolaminate or the silicon oxycarbonitride (SiOCN) nanolaminate havinga thickness of about 0.5 to about 10 nm.

The first deposition cycle 210 and the second deposition cycle 220 canbe repeated to form one or more of a silicon oxycarbide (SiOC)nanolaminate or silicon oxycarbonitride (SiOCN) nanolaminate having apredetermined thickness. In some embodiments, one or more of the firstdeposition cycle 210 and the second deposition cycle 220 are repeated toprovide one or more of a silicon oxycarbide (SiOC) nanolaminate orsilicon oxycarbonitride (SiOCN) nanolaminate having a thickness greaterthan about 1 nm, or in the range of about 1 nm to about 100 nm.

In some embodiments, the first process cycle is repeated m number oftimes and the second process cycle is repeated y number of times, wheren and y are independently in a range of from 1 to 20. Without intendingto be by bound by theory, it is thought that controlling the ratio ofthe number of repeats of the first deposition cycle 210 to the number ofrepeat of the second deposition cycle 220, the conformality and thecarbon content can be carefully controlled.

The post-processing operation 230 can be, for example, a process tomodify film properties (e.g., annealing) or a further film depositionprocess (e.g., additional ALD or CVD processes) to grow additionalfilms. In some embodiments, the post-processing operation 230 can be aprocess that modifies a property of the deposited film. In someembodiments, the post-processing operation 130 comprises annealing theas-deposited film. In some embodiments, annealing is done attemperatures in the range of about 300° C., 400° C., 500° C., 600° C.,700° C., 800° C., 900° C. or 1000° C. The annealing environment of someembodiments comprises one or more of an inert gas (e.g., molecularnitrogen (N₂), argon (Ar)) or a reducing gas (e.g., molecular hydrogen(H₂) or ammonia (NH₃)) or an oxidant, such as, but not limited to,oxygen (O₂), ozone (O₃), or peroxides. Annealing can be performed forany suitable length of time. In some embodiments, the film is annealedfor a predetermined time in the range of about 15 seconds to about 90minutes, or in the range of about 1 minute to about 60 minutes. In someembodiments, annealing the as-deposited film increases the density,decreases the resistivity and/or increases the purity of the film.

The method 200 can be performed at any suitable temperature dependingon, for example, the first silicon precursor, the second siliconprecursor, the oxidizing agent or thermal budget of the device. In someembodiments, exposures to the first silicon precursor (operation 212),the oxidizing agent (operation 216), and the second silicon precursor(operation 222), occur at the same temperature. In some embodiments, thesubstrate is maintained at a temperature in a range of about 200° C. toabout 650° C., or in the range of about 350° C. to about 500° C.

In some embodiments, exposure to the first silicon precursor (operation212) occurs at a different temperature than the exposure to theoxidizing agent (operation 216). In some embodiments, the substrate ismaintained at a first temperature in a range of about 300° C. to about650° C. for the exposure to the first silicon precursor, and at a secondtemperature in the range of about 200° C. to about 650° C. for exposurethe oxidizing agent. In some embodiments, the substrate may bemaintained at a third temperature in a range of about 250° C. to 500° C.for exposure to the second silicon precursor.

In the embodiment illustrated in FIG. 2, first deposition cycle 210 thesubstrate (or substrate surface) is exposed to the first siliconprecursor and the oxidizing agent sequentially. In another,un-illustrated, embodiment, the substrate (or substrate surface) isexposed to the first silicon precursor and the oxidizing agentsimultaneously in a CVD reaction.

In one or more embodiments, the silicon oxycarbide (SiOC) nanolaminatefilm has a carbon content of greater than or equal to about 5%, 7.5%,10%, 12.5 or 15%, on an atomic basis. In some embodiments, the siliconoxycarbide (SiOC) nanolaminate film comprises a carbon content in therange of about 2% to about 50%, or in the range of about 3% to about45%, or in the range of about 4% to about 40%, on an atomic basis. Insome embodiments, the silicon oxycarbide (SiOC) nanolaminate film has nonitrogen present.

In one or more embodiments, the silicon oxycarbonitride (SiOCN)nanolaminate film has a nitrogen content of greater than or equal toabout 0%, 5%, 7.5%, 10%, 12.5, or 15%, on an atomic basis. In someembodiments, the silicon oxycarbonitride (SiOCN) nanolaminate filmcomprises a nitrogen content in the range of about 0% to about 40%, orin the range of about 3% to about 35%, or in the range of about 4% toabout 30%, on an atomic basis.

According to one or more embodiments, the substrate is subjected toprocessing prior to and/or after forming the layer. This processing canbe performed in the same chamber or in one or more separate processingchambers. In some embodiments, the substrate is moved from the firstchamber to a separate, second chamber for further processing. Thesubstrate can be moved directly from the first chamber to the separateprocessing chamber, or it can be moved from the first chamber to one ormore transfer chambers, and then moved to the separate processingchamber. Accordingly, the processing apparatus may comprise multiplechambers in communication with a transfer station. An apparatus of thissort may be referred to as a “cluster tool” or “clustered system,” andthe like.

Generally, a cluster tool is a modular system comprising multiplechambers which perform various functions including substratecenter-finding and orientation, degassing, annealing, deposition and/oretching. According to one or more embodiments, a cluster tool includesat least a first chamber and a central transfer chamber. The centraltransfer chamber may house a robot that can shuttle substrates betweenand among processing chambers and load lock chambers. The transferchamber is typically maintained at a vacuum condition and provides anintermediate stage for shuttling substrates from one chamber to anotherand/or to a load lock chamber positioned at a front end of the clustertool. Two well-known cluster tools which may be adapted for the presentdisclosure are the Centura® and the Endura®, both available from AppliedMaterials, Inc., of Santa Clara, Calif. However, the exact arrangementand combination of chambers may be altered for purposes of performingspecific steps of a process as described herein. Other processingchambers which may be used include, but are not limited to, cyclicallayer deposition (CLD), atomic layer deposition (ALD), chemical vapordeposition (CVD), physical vapor deposition (PVD), etch, pre-clean,chemical clean, thermal treatment such as RTP, plasma nitridation,degas, orientation, hydroxylation and other substrate processes. Bycarrying out processes in a chamber on a cluster tool, surfacecontamination of the substrate with atmospheric impurities can beavoided without oxidation prior to depositing a subsequent film.

According to one or more embodiments, the substrate is continuouslyunder vacuum or “load lock” conditions, and is not exposed to ambientair when being moved from one chamber to the next. The transfer chambersare thus under vacuum and are “pumped down” under vacuum pressure. Inertgases may be present in the processing chambers or the transferchambers. In some embodiments, an inert gas is used as a purge gas toremove some or all of the reactants (e.g., reducing agent). According toone or more embodiments, a purge gas is injected at the exit of thedeposition chamber to prevent reactants (e.g., reducing agent) frommoving from the deposition chamber to the transfer chamber and/oradditional processing chamber. Thus, the flow of inert gas forms acurtain at the exit of the chamber.

The substrate can be processed in single substrate deposition chambers,where a single substrate is loaded, processed and unloaded beforeanother substrate is processed. The substrate can also be processed in acontinuous manner, similar to a conveyer system, in which multiplesubstrate are individually loaded into a first part of the chamber, movethrough the chamber and are unloaded from a second part of the chamber.The shape of the chamber and associated conveyer system can form astraight path or curved path. Additionally, the processing chamber maybe a carousel in which multiple substrates are moved about a centralaxis and are exposed to deposition, etch, annealing, cleaning, etc.processes throughout the carousel path.

During processing, the substrate can be heated or cooled. Such heatingor cooling can be accomplished by any suitable means including, but notlimited to, changing the temperature of the substrate support andflowing heated or cooled gases to the substrate surface. In someembodiments, the substrate support includes a heater/cooler which can becontrolled to change the substrate temperature conductively. In one ormore embodiments, the gases (either reactive gases or inert gases) beingemployed are heated or cooled to locally change the substratetemperature. In some embodiments, a heater/cooler is positioned withinthe chamber adjacent the substrate surface to convectively change thesubstrate temperature.

The substrate can also be stationary or rotated during processing. Arotating substrate can be rotated (about the substrate axis)continuously or in discrete steps. For example, a substrate may berotated throughout the entire process, or the substrate can be rotatedby a small amount between exposures to different reactive or purgegases. Rotating the substrate during processing (either continuously orin steps) may help produce a more uniform deposition or etch byminimizing the effect of, for example, local variability in gas flowgeometries.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the materials and methods discussed herein(especially in the context of the following claims) are to be construedto cover both the singular and the plural, unless otherwise indicatedherein or clearly contradicted by context. Recitation of ranges ofvalues herein are merely intended to serve as a shorthand method ofreferring individually to each separate value falling within the range,unless otherwise indicated herein, and each separate value isincorporated into the specification as if it were individually recitedherein. All methods described herein can be performed in any suitableorder unless otherwise indicated herein or otherwise clearlycontradicted by context. The use of any and all examples, or exemplarylanguage (e.g., “such as”) provided herein, is intended merely to betterilluminate the materials and methods and does not pose a limitation onthe scope unless otherwise claimed. No language in the specificationshould be construed as indicating any non-claimed element as essentialto the practice of the disclosed materials and methods.

Reference throughout this specification to “one embodiment,” “certainembodiments,” “one or more embodiments” or “an embodiment” means that aparticular feature, structure, material, or characteristic described inconnection with the embodiment is included in at least one embodiment ofthe disclosure. Thus, the appearances of the phrases such as “in one ormore embodiments,” “in certain embodiments,” “in one embodiment” or “inan embodiment” in various places throughout this specification are notnecessarily referring to the same embodiment of the disclosure.Furthermore, the particular features, structures, materials, orcharacteristics may be combined in any suitable manner in one or moreembodiments.

Although the disclosure herein has been described with reference toparticular embodiments, it is to be understood that these embodimentsare merely illustrative of the principles and applications of thepresent disclosure. It will be apparent to those skilled in the art thatvarious modifications and variations can be made to the method andapparatus of the present disclosure without departing from the spiritand scope of the disclosure. Thus, it is intended that the presentdisclosure include modifications and variations that are within thescope of the appended claims and their equivalents.

1. A method of depositing a film, the method comprising: exposing asubstrate in a processing chamber to a silicon precursor to deposit asilicon-containing film on the substrate, the silicon precursor having astructure of general formulae (Ia), (Ib), (Ic), or (Id)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl, X issilicon (Si) or carbon (C), Y is carbon (C) or oxygen (O); purging theprocessing chamber of the silicon precursor; exposing the substrate toan oxidant to react with the silicon-containing film to form one or moreof a silicon oxycarbide (SiOC) film or a silicon oxycarbonitride (SiOCN)film on the substrate, the oxidant comprising one or more of acarboxylic acid, an aldehyde, a ketone, an ethenediol, an oxalic acid, aglyoxylic acid, a peroxide, an alcohol, and a glyoxal; and purging theprocessing chamber of the oxidant.
 2. The method of claim 1, furthercomprising exposing the substrate to one or more of a strong oxidant oroxygen (O₂) plasma, the strong oxidant selected from one or more ofozone (O₃) and water (H₂O); and purging the processing chamber.
 3. Themethod of claim 2, wherein the plasma is a remote plasma.
 4. The methodof claim 2, wherein the plasma is a direct plasma.
 5. The method ofclaim 1, wherein the oxidant comprises a structure of Formula (II),Formula (III), Formula (IV), Formula (V), Formula (VI), Formula (VII),and Formula (VIII)

wherein R is selected from the group consisting of C₁-C₆ alkyl, C₁-C₆alkene, C₁-C₆ alkyne, C₅-C₈ aryl, and n is an integer from −1 to
 6. 6.The method of claim 1, wherein the silicon precursor comprises one ormore of bis(diethylamino)silane, bis(dimethylamine)silane,bis(dipropylamino)silane, dimethylamino diethylamino silane,tris(dimethylamino)silane, and tetrakis(dimethylamino)silane.
 7. Themethod of claim 1, wherein the silicon oxycarbide (SiOC) film or thesilicon oxycarbonitride (SiOCN) film has a K-value in a range of about2.0 to about 6.0.
 8. The method of claim 1, wherein purging theprocessing chamber comprises flowing a purge gas over the substrate. 9.The method of claim 8, wherein the purge gas is selected from one ormore of argon (Ar), nitrogen (N₂), or helium (He).
 10. The method ofclaim 1, wherein the silicon oxycarbide (SiOC) film or the siliconoxycarbonitride (SiOCN) film has a thickness greater than about 0.1 nm.11. A method of depositing a film, the method comprising: exposing asubstrate to a silicon precursor of general formulae (Ia), (Ib), (Ic),or (Id)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl, X issilicon (Si) or carbon (C), Y is carbon (C) or oxygen (O) to form asilicon-containing film; exposing the substrate to an oxidant to reactwith the silicon-containing film to form one or more of a siliconoxycarbide (SiOC) film or a silicon oxycarbonitride (SiOCN) film on thesubstrate; and exposing the substrate to one or more of a strong oxidantor oxygen (O₂) plasma, the strong oxidant selected from one or more ofozone (O₃) and water (H₂O).
 12. The method of claim 11, wherein theoxidant comprises a structure of Formula (II), Formula (III), Formula(IV), Formula (V), Formula (VI), Formula (VII), and Formula (VIII)

wherein R is selected from the group consisting of C₁-C₆ alkyl, C₁-C₆alkene, C₁-C₆ alkyne, C₅-C₈ aryl, and n is an integer from −1 to
 6. 13.The method of claim 11, wherein the silicon precursor comprises one ormore of bis(diethylamino)silane, bis(dimethylamine)silane,bis(dipropylamino)silane, dimethylamino diethylamino silane,tris(dimethylamino)silane, and tetrakis(dimethylamino)silane.
 14. Amethod of forming a nanolaminate, the method comprising: a firstdeposition cycle comprising: exposing a substrate to a first siliconprecursor of general formulae (Ia), (Ib), (Ic), and (Id):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are independently selectedfrom hydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, and substituted or unsubstituted vinyl to form asilicon-containing film, and exposing the substrate to an oxidant toreact with the silicon-containing film to form one or more of a siliconoxycarbide (SiOC) film or a silicon oxycarbonitride (SiOCN) film on thesubstrate; and a second deposition cycle comprising: exposing thesubstrate with one or more of the silicon oxycarbide (SiOC) film or thesilicon oxycarbonitride (SiOCN) film thereon to a second siliconprecursor having general formula (IXI) or general formula (X)

wherein X is silicon (Si) or carbon (C), Y is carbon (C) or oxygen (O),R⁹, R¹⁰, R¹¹, R¹² R¹³, R¹⁴, R¹⁵, and R¹⁶ are independently selected fromhydrogen (H), substituted or unsubstituted alkyl, substituted orunsubstituted alkoxy, substituted or unsubstituted vinyl, silane,substituted or unsubstituted amine, or halide to deposit a secondsilicon-containing film on the substrate, and exposing the substrate toa plasma to react with the second silicon-containing film to form one ormore of a silicon oxycarbide (SiOC) nanolaminate or a siliconoxycarbonitride (SiOCN) nanolaminate on the substrate.
 15. The method ofclaim 14, wherein the oxidant comprises a structure of Formula (II),Formula (III), Formula (IV), Formula (V), Formula (VI), Formula (VII),and Formula (VIII)

wherein R is selected from the group consisting of C₁-C₆ alkyl, C₁-C₆alkene, C₁-C₆ alkyne, C₅-C₈ aryl, and n is an integer from −1 to
 6. 16.The method of claim 14, wherein the silicon oxycarbide (SiOC)nanolaminate or the silicon oxycarbonitride (SiOCN) film has a K-valuein a range of about 2.0 to about 6.0.
 17. The method of claim 14,wherein the first deposition cycle further comprises exposing thesubstrate to one or more of a strong oxidant or oxygen (O₂) plasma, thestrong oxidant selected from one or more of ozone (O₃) or water (H₂O).18. The method of claim 14, wherein the plasma comprises one or more ofnitrogen (N₂), argon (Ar), helium (He), hydrogen (H₂), carbon monoxide(CO), or carbon dioxide (CO₂).
 19. The method of claim 14, furthercomprising repeating one or more of the first deposition cycle or thesecond deposition cycle to form one or more of the silicon oxycarbide(SiOC) nanolaminate or the silicon oxycarbonitride (SiOCN) nanolaminatehaving a thickness of about 0.5 to about 100 nm.
 20. The method of claim19, wherein the first deposition cycle is repeated m number of times andthe second deposition cycle is repeated y number of times, where n and yare independently in a range of from 1 to 20.